CN106702750A - Graphene-organosilicon modified urethane resin synthetic leather - Google Patents

Graphene-organosilicon modified urethane resin synthetic leather Download PDF

Info

Publication number
CN106702750A
CN106702750A CN201611262921.0A CN201611262921A CN106702750A CN 106702750 A CN106702750 A CN 106702750A CN 201611262921 A CN201611262921 A CN 201611262921A CN 106702750 A CN106702750 A CN 106702750A
Authority
CN
China
Prior art keywords
graphene
parts
organic silicon
polyurethane resin
modified polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201611262921.0A
Other languages
Chinese (zh)
Inventor
康伦国
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201611262921.0A priority Critical patent/CN106702750A/en
Publication of CN106702750A publication Critical patent/CN106702750A/en
Pending legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/142—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/005—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by blowing or swelling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/147—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the isocyanates used
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/04—Properties of the materials having electrical or magnetic properties
    • D06N2209/046—Anti-static
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/143—Inert, i.e. inert to chemical degradation, corrosion resistant
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties
    • D06N2209/1685—Wear resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The invention relates to a graphene-organosilicon modified urethane resin synthetic leather, which is prepared from the following ingredients: graphene-organosilicon modified urethane resin, fluorine-modified alkide resin, propylene glycol n-butyl ether, a flatting agent, a thickening agent, a foaming agent, a filler, a water-based color paste, a plasticizer, an ammonium stearate emulsion and de-ionized water, wherein the graphene-organosilicon modified urethane resin is prepared through reaction of polyisocyanate, polyhydric alcohol, a polybasic amine chain extender, oligomer polyhydric alcohol, dimethylolpropionic acid, organosilicon, graphene, a neutralizer and de-ionized water; the synthetic leather prepared by the invention is capable of effectively preventing statical electricity, and has the characteristics of good abrasion resistance, high crosslinking density, good chemical resistance and no pollution.

Description

A kind of Graphene-organic silicon modified polyurethane resin synthetic leather
Technical field
The present invention relates to a kind of synthetic leather and textile techniques, more particularly to a kind of Graphene-organic silicon modified polyurethane The formula of resins synthesis leather and the technology of technique, belong to synthetic leather and technical field of aqueous paint.
Background technology
In China, earliest artificial leather is the nitrocellulose varnished cloth of the Shanghai varnished cloth producers' cooperative production of the forties, from This has opened the prelude of China's artificial leather development.China is steady in yield and the gross output value as artificial leather synthetic leather big producer While growth, the pressure for facing is also increasing, and particularly with outlet, it is more and more harsher to environmental requirement, and this is to synthesis Leather manufacturing enterprise proposes baptism.
At present, artificial leather has been widely used for the clothes of people's daily life, shoes and hats gloves, case and bag, family's living furniture, text In the thousands of kinds such as lamp box advertisement, canopy lid, the automobile of change physical culture, industrial or agricultural and communications and transportation.
The synthetic leather point oiliness of China's production and aqueous two kinds, traditional solvent type polyurethane resin major part has with poisonous The organic solvents such as harmful dimethylformamide, toluene, acetone, butanone are used as decentralized medium, and these solvents at present can't be complete It is complete to reclaim, environmental pollution not only is caused at product end, and also serious harm employee is healthy in process of production.
Waterborne synthetic leather be mainly using aqueous polyurethane first coating is carried out in leather base cloth, then with contain calcium chloride Solidified in the aqueous solution, certain gas is had in the curing process and is produced, this feel to bass is had some improvement, but Effect on driving birds is not good.The typically all bass pad pasting of current oiliness and Waterborne synthetic leather is post-processed again, is primarily due to the wear-resisting of bass Not enough, but synthetic leather is by that can influence the feel, and cost to be also significantly increased after pad pasting, poor air permeability for fastness, and this is such product The maximum defect of product.Waterborne polyurethane artificial leather easily produces electrostatic simultaneously, and this brings necessarily to later stage factory process and consumption Puzzlement.
Damaged with to environment to solve the problems, such as that current oiliness synthetic leather is harmful, the present invention is using aqueous Synthetic leather, polyurethane resin can effectively improve the wearability of synthetic leather, and Graphene is introduced in aqueous polyurethane, can be effectively improved The electrostatic effect of synthetic leather.
Chinese patent CN105926308A is related to the formula and work of a kind of Graphene modified aqueous polyurethane production synthetic leather Although skill, this patent is also adopted by Graphene modified aqueous polyurethane, but its method for using physical blending, and the method is easy Cause the copolymerization of Graphene, it is impossible to the effective characteristic for playing Graphene, and its is relatively costly, the present invention is using Graphene, silicon Element chemistry modified aqueous polyurethane, this can not only obtain good wearability, moreover it is possible to improve the gloss of synthetic leather and bright-coloured Degree, this also can effectively solve synthetic leather and produce electrostatic problem.
The content of the invention
Organosilicon polymer resistant of high or low temperature is excellent, UV resistant, resistance to oxidation degraded, with low-surface-energy and thin well It is aqueous.Due to being free of Si-O keys in common polyurethane resin structure, and possess Si-O bond energys high in silicone molecules, its Si-O The firmness of key will be far above C-C, C-O key.The present invention introduces organosilicon in polyurethane resin, with organic-silicon-modified poly- ammonia Ester resin can improve its low-temperature flexibility, heat endurance, resistance to bond, hydrophobicity, ageing-resistant and antioxidative stabilizer etc..By Organic-silicon-modified polyurethane elastomer, will not fade because the environment such as outdoor high and low temperature weather change, harden, feeling like jelly etc. shows As even if still can for a long time keep its gay colours under the climatic environments such as intensive ultraviolet, ozone, rainwater and high temperature difference, outward See that architectural feature is permanent stablizes constant, the need for its anti-wear performance meets long-term frequency of use high.
Graphite can be prepared into graphite oxide after being aoxidized via strong oxidizer, and oxidized graphite flake layer contains substantial amounts of oxygen-containing pole Property group, such as hydroxyl, carboxyl, epoxy radicals, with specific surface area higher.Through peroxidating, its π-pi-conjugated structure suffers Graphene Destruction is arrived, intermolecular Van der Waals force is weak compared with Graphene, and lamella is easily peeled off, therefore graphene oxide is easily in the aqueous solution In fully peel away, formed stable homogeneous graphene oxide water solution, this is provided for Graphene modified aqueous polyurethane resin Natural endowment.
The purpose of the present invention aims to provide a kind of synthetic method of Graphene-organic silicon modified polyurethane resin.
Another object of the present invention aims to provide a kind of Graphene-organic silicon modified polyurethane resin and its a kind of wearability Good, pollution-free, antistatic and the low synthetic leather of surface tension.
In order to solve the problems, such as techniques as described above, the present invention takes following technical scheme：The present invention relates to one kind it is wear-resisting, The Waterborne synthetic leather coating of antistatic, by weight percentage, consisting of：Graphene-organic silicon modified polyurethane resin 35.0~50.0 parts, 20.0~35.0 parts of fluorine richness alkyd resin, 3.0~8.0 parts of propylene glycol monobutyl ether, levelling agent 0.5~1.5 Part, 1.0~3.0 parts of thickener, 0.5~2.0 part of foaming agent, 3.0~8.0 parts of filler, 0~5.0 part of aqueous color paste, plasticizer 8.0~12.0 parts, 2.0~6.0 parts of ammonium stearate emulsion, 6.0~10.0 parts of deionized water.
Described filler is the mixture of one or more arbitrary proportions in calcium carbonate, diatomite, kaolin.
Described plasticizer is o-phthalic acid dibutyl ester, dibutyl phthalate, SA dioctyl ester, epoxy soybean Oil, tributyl 2-acetylcitrate, hexamethylene 1, the mixture of one or more arbitrary proportions in 2- dioctyl phthalate diisononyl esters.
The ammonium stearate emulsion includes component：Stearic acid, ammoniacal liquor, lauryl sodium sulfate, water.
The present invention proposes the technique that a kind of Graphene-organic silicon modified polyurethane resin produces synthetic leather, including as follows Step：
A, prepared coating liquid, by Graphene-organic silicon modified polyurethane resin, fluorine richness alkyd resin, propyleneglycol monobutyl Ether, levelling agent, foaming agent, filler, aqueous color paste, plasticizer, ammonium stearate emulsion, deionized water are put into according to formula rate Container, is disperseed with mixer, is filtered after stirring, and adds appropriate thickener regulation viscosity；
B, the coating solution that will be prepared are made coating foams by Intelligent Dynamic foam maker, then by coating foams It is coated onto in leather base cloth；
After the completion of C, coating, oven for drying is placed on, that is, obtains Graphene-organic silicon modified polyurethane resin foaming Bass.
Graphene-organic silicon modified polyurethane resin of the present invention, mainly by polyisocyanates, polyalcohol, polynary Amine chain extender, oligomer polyol, dihydromethyl propionic acid, organosilicon, dibutyl tin laurate, Graphene, nertralizer and Deionized water is constituted.
Described Graphene-organic silicon modified polyurethane resin, it is characterised in that：By weight percentage, consisting of： 8.0~22.0 parts of polyisocyanates, 2.0~7.0 parts of polyalcohol, 0.5~2.0 part of polynary amine chain extender, oligomer polyol 4.0~12.0 parts, 1.5~4.5 parts of dihydromethyl propionic acid, 1.0~5.0 parts of organosilicon, dibutyl tin laurate 0.01~0.1 Part, 0.5~2.5 part of Graphene, 4.0~10.0 parts of acetone, 1.0~3.0 parts of nertralizer, 48.0~68.0 parts of deionized water.
Described polyalcohol is ethylene glycol, propane diols, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, a contracting DPG, 2-butyl-2-ethyl-1,3-propanediol, 2,4- diethyl -1,5- pentanediols, 2- ethyl -1,3- hexylene glycols, three The combination of one or more in hydroxymethyl-propane, glycerine, trimethylolethane, pentaerythrite, xylitol, sorbierite.
Described oligomer polyol is polytetrahydrofuran polyol, makrolon of the molecular weight between 1000~4000 In polyalcohol, polycaprolactone polyol, polyethylene oxide polyol, polyether Glycols, polyethylene glycol, polyoxypropylene polyol The combination of one or more.
Described Graphene be hydroxyl graphene oxide, by Hummers methods, Staudemaier methods, electrochemical process or It is prepared by Brodie methods；Further, it is the graphene oxide of Hummers methods preparation.
Described organic silicon monomer is hydroxy-end capped dimethyl silicone polymer, the dimethyl silicone polymer of hydroxyl alkyl end-blocking The combination of one or more in the dimethyl silicone polymer blocked with hydroxy polyethers.
Described nertralizer is the combination of one or more in triethylamine, ammoniacal liquor, dimethylethanolamine.
Described polynary amine chain extender is ethylenediamine, the hydrazine of adipic acid two, hydrazine hydrate, N, N- dihydroxy (diisopropyl) benzene The combination of one or more in amine.
Described polyisocyanates is toluene di-isocyanate(TDI) TDI, IPDI IPDI, hexa-methylene two Isocyanates HDI, XDI XDI, cyclohexanedimethyleterephthalate diisocyanate H6XDI, durol two The combination of one or more in methylene diisocyanate TMXDI.
Obtained a kind of Graphene-organic silicon modified polyurethane resin of the invention, is characterized in that wearability is good, static electricity resistance The excellent, crosslink density of energy is high, corrosion resistance and good.
Specific embodiment
The present invention combines system of the following instance to wear-resisting, antistatic Graphene-organic silicon modified polyurethane resin emulsion It is standby to be further described.
Embodiment 1
A kind of Graphene-organic silicon modified polyurethane resin, its preparation technology is as follows：
A, in equipped with thermometer, condenser pipe, four mouthfuls of reactors of agitator, by formula percentage by weight, successively plus Enter 3.0 parts of butanediol, 1.5 parts of trimethylolpropane, 1.5 parts of Graphene, 6.0 parts of polytetrahydrofuran polyol, dihydroxymethyl third 2.6 parts of acid, 1.5~2.0h of vacuum dehydration between being heated to 95~110 DEG C；
B, a, in equipped with thermometer, condenser pipe, four mouthfuls of reactors of agitator, by formula percentage by weight, successively Add 3.0 parts of butanediol, 1.5 parts of trimethylolpropane, 1.5 parts of Graphene, 6.0 parts of polytetrahydrofuran polyol, dihydroxymethyl 2.6 parts of propionic acid, 1.5~2.0h of vacuum dehydration between being heated to 95~110 DEG C；
C, continuation stirring cool the temperature to less than 40 DEG C, are slowly added dropwise 1.9 parts of nertralizer triethylamine, continue stirring reaction 15 ~20min, adds 58.25 parts of the water of amount of calculation, continues to stir 15min, 1.2 parts of ethylenediamine is added under agitation, at a high speed Dispersed with stirring 1h, then stirring at low speed 0.5h, steams de- acetone under decompression, i.e., prepared a kind of Graphene-organic silicon modified aqueous poly- Urethane Resin A.
Embodiment 2
A kind of Graphene-organic silicon modified polyurethane resin, its preparation technology is as follows：
A, in equipped with thermometer, condenser pipe, four mouthfuls of reactors of agitator, by formula percentage by weight, successively plus Enter 3.2 parts of neopentyl glycol, 1.2 parts of trimethylolpropane, 1.6 parts of Graphene, 5.5 parts of polytetrahydrofuran polyol, dihydroxymethyl 2.4 parts of propionic acid, 1.5~2.0h of vacuum dehydration between being heated to 95~110 DEG C；
B, it is cooled to 60~70 DEG C and adds hydroxy-end capped 2.5 parts of dimethyl silicone polymers, toluene di-isocyanate(TDI) is added dropwise 15.0 parts, in 0.5~1h completion of dropping；Then be added dropwise 0.05 part of dibutyl tin laurate, be warming up to 80~82 DEG C reaction 2~ 2.5h, adds 6.5 parts of acetone, determines nco value, the terminating reaction when the value for determining is close with Theoretical Design value；
C, continuation stirring cool the temperature to less than 40 DEG C, are slowly added dropwise 2.0 parts of nertralizer triethylamine, continue stirring reaction 10 ~20min, adds 58.45 parts of the water of amount of calculation, continues to stir 15min, 1.6 parts of ethylenediamine is added under agitation, at a high speed Dispersed with stirring 1h, then stirring at low speed 0.5h, steams de- acetone under decompression, i.e., prepared a kind of Graphene-organic silicon modified aqueous poly- Urethane resin B.
Embodiment 3
A kind of technique of Graphene-organic silicon modified polyurethane resin synthetic leather, comprises the following steps：
A, prepared coating liquid, by Graphene-organic silicon modified polyurethane resin A40.0 parts, fluorine richness alkyd resin 25.0 Part, 4.0 parts of propylene glycol monobutyl ether, 0.8 part of levelling agent, 1.2 parts of foaming agent, 5.0 parts of filler, 2.0 parts of aqueous color paste, plasticizer 10.0 parts, 4.0 parts of ammonium stearate emulsion, 6.5 parts of deionized water proportionally add container, disperseed with mixer, stir After filter, add 1.5 parts of thickener regulation viscosity；
B, the coating solution that will be prepared are made coating foams by Intelligent Dynamic foam maker, then by coating foams It is coated onto in leather base cloth；
After the completion of C, coating, oven for drying is placed on, that is, obtains Graphene-organic silicon modified polyurethane resin foaming Bass.
Embodiment 4
A kind of Graphene-organic silicon modified polyurethane resin produces the technique of synthetic leather, comprises the following steps：
A, prepared coating liquid, by Graphene -46.0 parts of organic silicon modified polyurethane resin B, fluorine richness alkyd resin 20.0 Part, 3.5 parts of propylene glycol monobutyl ether, 1.0 parts of levelling agent, 1.5 parts of foaming agent, 4.0 parts of filler, 1.0 parts of aqueous color paste, plasticizer 8.5 parts, 4.5 parts of ammonium stearate emulsion, 8.0 parts of deionized water add container according to formula rate, disperseed with mixer, stirring is equal Filtering after even, adds 2.0 parts of regulation viscosity of thickener；
B, the coating solution that will be prepared are made coating foams by Intelligent Dynamic foam maker, then by coating foams It is coated onto in leather base cloth；
After the completion of C, coating, oven for drying is placed on, that is, obtains Graphene-organic silicon modified polyurethane resin foaming Bass.
Although the present invention has been explained in detail and has been cited embodiment, for one of ordinary skill in the art, show So can as specified above and make various schemes, modification and change, should be construed as being included within the scope of claim.

Claims (8)

1. a kind of Graphene-organic silicon modified polyurethane resin synthetic leather, it is characterised in that：By weight percentage, its composition For：35.0~50.0 parts of Graphene-organic silicon modified polyurethane resin, 20.0~35.0 parts of fluorine richness alkyd resin, propane diols 3.0~8.0 parts of monobutyl ether, 0.5~1.5 part of levelling agent, 1.0~3.0 parts of thickener, 0.5~2.0 part of foaming agent, filler 3.0 ~8.0 parts, 0~5.0 part of aqueous color paste, 8.0~12.0 parts of plasticizer, 2.0~6.0 parts of ammonium stearate emulsion, deionized water 6.0 ~10.0 parts；
One of which Graphene-organic silicon modified polyurethane resin produces the technique of synthetic leather, comprises the following steps：
A) prepared coating liquid, by Graphene-organic silicon modified polyurethane resin, fluorine richness alkyd resin, propylene glycol monobutyl ether, stream Flat agent, foaming agent, filler, aqueous color paste, plasticizer, ammonium stearate emulsion, deionized water are put into container according to formula rate, Disperseed with mixer, filtered after stirring, add appropriate thickener regulation viscosity；
B) coating solution that will be prepared is made coating foams by Intelligent Dynamic foam maker, then coating foams are coated onto In leather base cloth；
C) after the completion of applying, oven for drying is placed on, that is, obtains Graphene-organic silicon modified polyurethane resin foaming shellfish This.
Wherein, described Graphene-organic silicon modified polyurethane resin, is mainly expanded by polyisocyanates, polyalcohol, polynary amine Chain agent, oligomer polyol, dihydromethyl propionic acid, organosilicon, dibutyl tin laurate, Graphene, nertralizer and deionization Water is constituted.
2. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 1, it is characterised in that：Percentage by weight Than meter, consisting of：8.0~22.0 parts of polyisocyanates, 2.0~7.0 parts of polyalcohol, polynary amine chain extender 0.5~2.0 Part, 4.0~12.0 parts of oligomer polyol, 1.5~4.5 parts of dihydromethyl propionic acid, 1.0~5.0 parts of organosilicon, tin dilaurate two 0.01~0.1 part of butyl tin, 0.5~2.5 part of Graphene, 4.0~10.0 parts of acetone, 1.0~3.0 parts of nertralizer, deionized water 48.0~68.0 parts.
3. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described is polynary Alcohol is ethylene glycol, propane diols, butanediol, hexylene glycol, neopentyl glycol, Diethylene Glycol, dipropylene glycol, 2- butyl -2- Ethyl -1,3- propane diols, 2,4- diethyl -1,5- pentanediols, 2- ethyl -1,3- hexylene glycols, trimethylolpropane, glycerine, three The combination of one or more in hydroxymethyl ethane, pentaerythrite, xylitol, sorbierite.
4. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described is oligomeric Thing polyalcohol is many polytetrahydrofuran polyol of the molecular weight between 1000~4000, polycarbonate polyol, polycaprolactone The group of one or more in first alcohol, polyethylene oxide polyol, polyether Glycols, polyethylene glycol, polyoxypropylene polyol Close.
5. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described graphite Alkene is hydroxyl graphene oxide, is prepared by Hummers methods, Staudemaier methods, electrochemical process or Brodie methods；Further, For graphene oxide prepared by Hummers methods.
6. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described is organic Silicon monomer is the poly- of hydroxy-end capped dimethyl silicone polymer, the dimethyl silicone polymer of hydroxyl alkyl end-blocking and hydroxy polyethers end-blocking The combination of one or more in dimethyl siloxane.
7. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described is polynary Amine chain extender be ethylenediamine, the hydrazine of adipic acid two, hydrazine hydrate, N, in N- dihydroxy (diisopropyl) aniline one or more Combination.
8. a kind of Graphene-organic silicon modified polyurethane resin as claimed in claim 2, it is characterised in that：Described polyisocyanate Cyanate is toluene di-isocyanate(TDI) TDI, IPDI IPDI, hexamethylene diisocyanate HDI, the Asia of benzene two Methyl diisocyanate XDI, cyclohexanedimethyleterephthalate diisocyanate H6XDI, tetramethylxylylene diisocyanate The combination of one or more in TMXDI.
CN201611262921.0A 2016-12-30 2016-12-30 Graphene-organosilicon modified urethane resin synthetic leather Pending CN106702750A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611262921.0A CN106702750A (en) 2016-12-30 2016-12-30 Graphene-organosilicon modified urethane resin synthetic leather

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611262921.0A CN106702750A (en) 2016-12-30 2016-12-30 Graphene-organosilicon modified urethane resin synthetic leather

Publications (1)

Publication Number Publication Date
CN106702750A true CN106702750A (en) 2017-05-24

Family

ID=58906833

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611262921.0A Pending CN106702750A (en) 2016-12-30 2016-12-30 Graphene-organosilicon modified urethane resin synthetic leather

Country Status (1)

Country Link
CN (1) CN106702750A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107880526A (en) * 2017-11-14 2018-04-06 东莞市鑫益电子科技有限公司 A kind of preparation method of graphene modified polyurethane material
CN107904960A (en) * 2017-10-28 2018-04-13 长沙秋点兵信息科技有限公司 Preparation method of smooth artificial synthetic leather
CN108034334A (en) * 2017-12-29 2018-05-15 中科院广州化学有限公司 A kind of waterborne organic silicon fluorine richness graphene oxide/epoxy coating and preparation method thereof
CN108193506A (en) * 2018-02-02 2018-06-22 天守(福建)超纤科技股份有限公司 A kind of automotive trim graphene superfine fiber chemical leather
CN109021907A (en) * 2018-09-03 2018-12-18 孙桂芝 A kind of preparation method of use for synthetic leather high-adhesion aqueous polyurethane adhesive
CN109161327A (en) * 2018-07-11 2019-01-08 无锡市惠诚石墨烯技术应用有限公司 Modified urethane water-repellent paint of a kind of graphene oxide and preparation method thereof
WO2019095642A1 (en) * 2017-11-20 2019-05-23 曹熙辰 Anti-corrosion coating composition, method for preparing anti-corrosion coating, and anti-corrosion coating
CN111746056A (en) * 2020-07-08 2020-10-09 清远市齐力合成革有限公司 Organic silicon modified high-wear-resistance synthetic leather
CN116143994A (en) * 2022-12-29 2023-05-23 广州海豚新材料有限公司 Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880969A (en) * 2010-07-15 2010-11-10 江苏宝泽高分子材料股份有限公司 Veneering dry-kneading hairy crazy horse resin for synthetic leather and preparation method thereof
CN102532461A (en) * 2011-12-23 2012-07-04 上海汇得化工有限公司 Wet process polyurethane resin used for highly elastic water absorption basketball leather and preparation method
CN102604026A (en) * 2011-02-17 2012-07-25 浙江深蓝轻纺科技有限公司 Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof
CN105385148A (en) * 2015-12-04 2016-03-09 浙江华峰合成树脂有限公司 Sulfonated graphene-modified waterborne polyurethane resin and preparation method thereof
CN105926308A (en) * 2016-05-12 2016-09-07 宋婷婷 Formula and technology for producing synthetic leather from graphene modified waterborne polyurethane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101880969A (en) * 2010-07-15 2010-11-10 江苏宝泽高分子材料股份有限公司 Veneering dry-kneading hairy crazy horse resin for synthetic leather and preparation method thereof
CN102604026A (en) * 2011-02-17 2012-07-25 浙江深蓝轻纺科技有限公司 Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof
CN102532461A (en) * 2011-12-23 2012-07-04 上海汇得化工有限公司 Wet process polyurethane resin used for highly elastic water absorption basketball leather and preparation method
CN105385148A (en) * 2015-12-04 2016-03-09 浙江华峰合成树脂有限公司 Sulfonated graphene-modified waterborne polyurethane resin and preparation method thereof
CN105926308A (en) * 2016-05-12 2016-09-07 宋婷婷 Formula and technology for producing synthetic leather from graphene modified waterborne polyurethane

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107904960A (en) * 2017-10-28 2018-04-13 长沙秋点兵信息科技有限公司 Preparation method of smooth artificial synthetic leather
CN107880526A (en) * 2017-11-14 2018-04-06 东莞市鑫益电子科技有限公司 A kind of preparation method of graphene modified polyurethane material
WO2019095642A1 (en) * 2017-11-20 2019-05-23 曹熙辰 Anti-corrosion coating composition, method for preparing anti-corrosion coating, and anti-corrosion coating
CN108034334A (en) * 2017-12-29 2018-05-15 中科院广州化学有限公司 A kind of waterborne organic silicon fluorine richness graphene oxide/epoxy coating and preparation method thereof
CN108034334B (en) * 2017-12-29 2020-01-17 中科院广州化学有限公司 Water-based organic silicon-fluorine modified graphene oxide/epoxy resin coating and preparation method thereof
CN108193506A (en) * 2018-02-02 2018-06-22 天守(福建)超纤科技股份有限公司 A kind of automotive trim graphene superfine fiber chemical leather
CN109161327A (en) * 2018-07-11 2019-01-08 无锡市惠诚石墨烯技术应用有限公司 Modified urethane water-repellent paint of a kind of graphene oxide and preparation method thereof
CN109021907A (en) * 2018-09-03 2018-12-18 孙桂芝 A kind of preparation method of use for synthetic leather high-adhesion aqueous polyurethane adhesive
CN111746056A (en) * 2020-07-08 2020-10-09 清远市齐力合成革有限公司 Organic silicon modified high-wear-resistance synthetic leather
CN116143994A (en) * 2022-12-29 2023-05-23 广州海豚新材料有限公司 Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather
CN116143994B (en) * 2022-12-29 2023-09-15 广州海豚新材料有限公司 Aqueous organosilicon modified polyurethane dispersoid, preparation method thereof, synthetic leather surface layer containing aqueous organosilicon modified polyurethane dispersoid and luggage leather

Similar Documents

Publication Publication Date Title
CN106702750A (en) Graphene-organosilicon modified urethane resin synthetic leather
CN107903357B (en) Fluorine-containing polyurethane modified acrylic acid water-based resin and preparation method thereof
CN106590399A (en) Graphene-organosilicone modified polyurethane water-based paint
CN106867354B (en) A kind of graphene-fluorine richness polyurethane resin aqueous functional coating
CN104194610B (en) Self-crosslinked one-component polyurethane waterproofing coating
CN106220817B (en) A kind of no-solvent type interior leather for automobiles middle layer polyurethane resin and preparation method thereof
CN106700019A (en) Melamine-modified waterborne polyurethane flame-retarded resin and preparation method thereof
CN106632965A (en) Graphene-organosilicon modified waterborne polyurethane resin
CN105566599B (en) A kind of aqueous polyurethane emulsion and preparation method thereof for apolar surfaces coating
CN109438643A (en) A kind of biology base fluorine modified aqueous polyurethane resin and preparation method thereof
CN106397722A (en) Carbon fiber modified non-solvent polyurethane surface layer resin for sports shoe leather, as well as preparation method and application of carbon fiber modified non-solvent polyurethane surface layer resin
CN109898342B (en) Preparation method of scratch-resistant synthetic leather based on high-resilience waterborne polyurethane
CN107936814B (en) POSS (polyhedral oligomeric silsesquioxane) modified high-hardness polyurethane odor-free wood lacquer
CN107903358A (en) Solvent-free self-crosslinking modified aqueous polyurethane resin for printing in textiles
CN103805122A (en) Waterborne polyurethane patch adhesive and preparation method thereof
CN108517029A (en) A kind of soft use for synthetic leather non yellowing type no-solvent polyurethane intermediate layer resin and the preparation method and application thereof
CN106832138A (en) A kind of Graphene fluorine modified aqueous polyurethane resin and preparation method thereof
CN109439169A (en) A kind of aqueous clear finish of biology base light with lotus leaf effect
CN112646114A (en) Triplecene derivative modified polyurethane aqueous resin and preparation method thereof
CN110746571A (en) APAO modified polyurethane waterborne resin and preparation method thereof
CN106928428A (en) Aqueous polyurethane emulsion and preparation method thereof
CN112080185A (en) Waterborne polyurethane industrial paint and preparation method thereof
CN113698853B (en) Coating and preparation method and application thereof
CN106633013B (en) A kind of graphene modified water-soluble silanol acid resin and preparation method thereof
CN117417488A (en) Acrylic acid modified waterborne polyurethane dispersoid and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170524